Method of making heat treatable coated article with protective layer

ABSTRACT

A soda inclusive glass substrate is coated with a highly tetrahedral amorphous carbon inclusive layer that is a form of diamond-like carbon (DLC). In certain embodiments, the amorphous carbon layer includes at least about 35% sp 3  carbon-carbon bonds, more preferably at least about 70%, and most preferably at least about 80% of the sp 3  carbon-carbon bonds. The high density (e.g. greater than or equal to about 2.4 gm/cm 3 ) of the amorphous carbon layer prevents soda from exiting the glass and reacting with water at surface(s) of the glass, thereby minimizing visible stains (or corrosion) on the glass. The high density amorphous carbon layer also may repel water. In some embodiments, the highly tetrahedral amorphous carbon layer is part of a larger DLC coating, while in other embodiments the highly tetrahedral layer forms the entirety of a DLC coating on the substrate.

This invention relates to a diamond-like carbon (DLC) coating providedon (directly or indirectly) a glass or other substrate. Moreparticularly, in certain preferred embodiments, this invention relatesto a highly tetrahedral amorphous diamond like carbon coating on a sodainclusive glass substrate (e.g. on a soda lime silica glass substrate)for purposes of repelling water and/or reducing corrosion on the coatedarticle. Ion beam and filtered carbon cathodic arc deposition arepreferred methods of deposition for the coating.

BACKGROUND OF THE INVENTION

Soda inclusive glasses are known in the art. For example, see U.S. Pat.No. 5,214,008, which is hereby incorporated herein by reference.

Soda lime silica glass, for example, is used for architectural glass,automotive windshields, and the like. The aforesaid '008 patentdiscloses one type of soda lime silica glass known in the art.

Unfortunately, conventional soda inclusive glasses are susceptible toenvironmental corrosion which occurs when sodium (Na) diffuses from orleaves the glass interior. This sodium, upon reaching the surface of theglass, may react with water to produce visible stains or smears (e.g.stains of sodium hydroxide) on the glass surface. Such glasses are alsosusceptible to retaining water on their surfaces in many differentenvironments, including when used as automotive windows (e.g. backlites,side windows, and/or windshields). These glasses are also susceptible tofogging up on the interior surface thereof in automotive and otherenvironments.

In view of the above, it is apparent that there exists a need in the artto prevent and/or minimize visible stains/corrosion on soda inclusivecoated glass surfaces. There also exists a need in the art to provide astrong protective coating on window substrates. Other needs in the artinclude the need for a coating on glass that reduces the coatedarticle's susceptibility to fogging up in automotive and otherenvironments, and the need for a coated glass article that can repelwater and/or dirt.

It is known to provide diamond like carbon (DLC) coatings on glass. U.S.Pat. No. 5,637,353, for example, states that DLC may be applied onglass. The '353 patent teaches that because there is a bonding problembetween glass and that type of DLC, an intermediate layer is providedtherebetween. Moreover, the '353 patent does not disclose or mention thehighly tetrahedral amorphous type of DLC used in many embodiments setforth below. The DLC of the '353 patent would not be an efficientcorrosion minimizer on glass in many instances due to its low density(likely less than 2.0 gm/cm³). Still further, the DLC of the '353 patentis deposited in a less than efficient manner for certain embodiments ofthis invention.

It is known that many glass substrates have small cracks defined intheir surface. The stress needed to crack glass typically decreases withincreasing exposure to water. When water enters such a crack, it causesinteratomic bonds at the tip of the crack to rupture. This weakensglass. Water can accelerate the rate of crack growth more than athousand times by attacking the structure of the glass at the root ortip of the crack. Strength of glass is in part controlled by the growthof cracks that penetrate the glass. Water, in these cracks, reacts withglass and causes it to crack more easily as described in “The Fracturingof Glass,” by T. A. Michalske and Bruce C. Bunker, hereby incorporatedherein by reference. Water molecules cause a concerted chemical reactionin which a silicon-oxygen bond (of the glass) at the crack tip and onoxygen-hydrogen bond in the water molecule are both cleaved, producingtwo silanol groups. The length of the crack thus increases by one bondrupture, thereby weakening the glass. Reaction with water lowers theenergy needed to break the silicon-oxygen bonds by a factor of about 20,and so the bond-rupture allows glass cracks to grow faster.

Thus, there also exists a need in the art for preventing water fromreaching silicon-oxygen bonds at tips of cracks in a glass substrate, soas to strengthen the glass.

It is a purpose of different embodiments of this invention to fulfillany or all of the above described needs in the art, and/or other needswhich will become apparent to the skilled artisan once given thefollowing disclosure.

SUMMARY OF THE INVENTION

An object of this invention is to provide a coated article that can shedwater (e.g. automotive windshield, automotive backlite, automotive sidewindow, architectural window, etc.).

Another object of this invention is to provide a system or means forreducing or minimizing corrosion on soda inclusive coated glassarticles.

Another object of this invention is to provide a coated glass articlewherein a DLC coating protects the glass from acids such as HF, nitric,and sodium hydroxide (the coating may be chemically inert).

Another object of this invention is to provide a coated glass articlethat is not readily susceptible to fogging up.

Another object is to provide a barrier layer with no pin holes on aglass substrate.

Another object of this invention is to provide a coated glass articlethat is abrasion resistant, and/or can repel dirt and the like.

Another object of this invention is to provide a glass substrate with aDLC coating inclusive of a highly tetrahedral dense amorphous carbonlayer, either in direct or indirect contact with the substrate.

Another object of this invention is to provide a DLC coating on asubstrate, wherein the coating includes different portions or layerswith different densities and different sp³ carbon-carbon bondpercentages. The ratio of sp³ to sp² carbon-carbon bonds may bedifferent in different layers or portions of the coating. Such a coatingwith varying compositions therein may be continuously formed by varyingthe ion energy used in the deposition process so that stresses in thecoating are reduced in the interfacial portion/layer of the DLC coatingimmediately adjacent the underlying substrate. Thus, a DLC coating mayhave therein an interfacial layer with a given density and sp³carbon-carbon bond percentage, and another layer with a higher densityand higher sp³ carbon-carbon bond percentage.

Generally speaking, this invention fulfills certain of the abovedescribed needs/objects in the art by providing a coated glasscomprising:

a glass substrate including at least about 5% by weight soda/Na₂O;

an amorphous carbon layer provided on the glass substrate in order toreduce corrosion or stains on the coated glass, wherein said amorphouscarbon layer includes sp² and sp³ carbon-carbon bonds; and

wherein the amorphous carbon layer has more sp³ carbon-carbon bonds thansp² carbon-carbon bonds.

In other embodiments, this invention fulfills certain of the abovedescribed needs in the art by providing a coated glass comprising:

a soda inclusive glass substrate comprising, on a weight basis, fromabout 60-80% SiO₂, from about 10-20% Na₂O, from about 0-16% CaO, fromabout 0-10% K₂O, from about 0-10% MgO, and from about 0-5% Al₂O₃; and

a non-crystalline diamond-like carbon (DLC) coating is provided on theglass substrate, wherein the DLC coating includes at least one highlytetrahedral amorphous carbon layer having at least about 35% sp³carbon-carbon bonds.

In certain embodiments, the glass substrate is a soda lime silica floatglass substrate.

In preferred embodiments, the entire DLC coating or alternatively only alayer within the DLC coating, has a density of from about 2.4 to 3.4gm/cm³, most preferably from about 2.7 to 3.0 gm/cm³.

In certain embodiments, the tetrahedral amorphous carbon layer has theaforesaid density range and includes at least about 70% sp³carbon-carbon bonds, and most preferably at least about 80% sp³carbon-carbon bonds.

In certain embodiments, the DLC coating includes a top layer (e.g. fromabout 2 to 8 atomic layers, or less than about 20 Å) that is less densethan other portions of the DLC coating, thereby providing a solidlubricant portion at the top surface of the DLC coating. Layeredgraphene connected carbon atoms are provided in this thin layer portion.The coefficient of friction is less than about 0.1 for this thin layerportion.

Another advantage of this invention is that the temperature of the glasssubstrate is less than about 200° C., preferably less than about 150°C., most preferably from about 60-80° C., during the deposition of DLCmaterial. This is to minimize graphitization during the depositionprocess.

This invention further fulfills the above described needs in the art byproviding a window having a substrate and a highly tetrahedral amorphouscarbon layer thereon, wherein the substrate is or includes at least oneof borosilicate glass, soda lime silica glass, and plastic.

This invention will now be described with respect to certain embodimentsthereof, along with reference to the accompanying illustrations.

IN THE DRAWINGS

FIG. 1 is a side cross sectional view of a coated article according toan embodiment of this invention, wherein a substrate is provided with aDLC coating including at least two layers therein.

FIG. 2 is a side cross sectional view of a coated article according toanother embodiment of this invention, wherein a highly tetrahedralamorphous carbon DLC coating is provided on and in contact with asubstrate.

FIG. 3 is a side cross sectional view of a coated article according toyet another embodiment of this invention wherein a low-E or othercoating is provided on a substrate, with the DLC coating of either ofthe FIG. 1 or FIG. 2 embodiments also on the substrate but over top ofthe intermediate low-E or other coating.

FIG. 4 illustrates an exemplar sp³ carbon atom hybridization bond.

FIG. 5 illustrates an exemplar sp² carbon atom hybridization bond.

FIG. 6 illustrates exemplar sp hybridizations of a carbon atom.

FIG. 7 is a side cross sectional view of carbon ions penetrating thesubstrate or DLC surface so as to strongly bond a DLC layer according toany embodiment herein.

FIG. 8 is a side cross sectional view of a coated glass substrateaccording to an embodiment of this invention, illustrating DLC bondspenetrating cracks in the surface of a glass substrate.

DETAILED DESCRIPTION OF CERTAIN EMBODIMENTS OF THIS INVENTION

Referring now more particularly to the accompanying drawings in whichlike reference numerals indicate like elements throughout theaccompanying views.

FIG. 1 is a side cross sectional view of a coated glass articleaccording to an embodiment of this invention, wherein at least onediamond-like carbon (DLC) protective coating(s) 3 is provided directlyon soda-inclusive glass substrate 1. DLC coating 3 in the FIG. 1embodiment includes at least one highly tetrahedral amorphous carbon(ta-C) layer 7 that has a high density (e.g. greater than about 2.4grams per cubic centimeter) and functions to repel water and seal sodawithin the soda inclusive glass substrate. Coating 3 further includes atleast one interfacing layer 8 directly adjacent substrate 1, where layer8 has a lesser density and a lesser percentage of sp³ carbon-carbonbonds than ta-C layer 7. Even though layer 8 differs from layer 7 inthese manner(s), interfacing layer 8 may or may not qualify as ta-C witha density of at least about 2.4 gm/cm³, as described below. It is notedthat in certain embodiments, coating 3 may include multiple ta-C layers7 and/or multiple layers 8. Layers 7 and 8 of the coating may be formedin a continuous or non-continuous deposition process in differentembodiments of this invention.

FIG. 2 is a side cross sectional view of a coated glass articleaccording to another embodiment of this invention, wherein at least oneDLC coating(s) 3 is provided on glass substrate 1. In the FIG. 2embodiment, substantially the entire DLC coating 3 is made up of highlytetrahedral amorphous carbon (ta-C), similar to layer 7, having adensity of at least about 2.4 grams per cubic centimeter and a highpercentage (e.g. at least about 35%, more preferably at least about 70%,and most preferably at least about 80%) of sp³ carbon-carbon bonds. Inother words, ta-C layer 7 from the FIG. 1 embodiment forms the entiretyof DLC coating 3 in the FIG. 2 embodiment. DLC coating 3 in the FIG. 2embodiment may or may not have equal densities and/or the samepercentages of sp³ carbon-carbon bonds throughout the thickness ofcoating 3, as these parameters may be varied throughout layers 3, 7 and8 in the FIGS. 1 and 2 embodiments by changing the ion energy usedduring the deposition process of coating 3.

In the FIG. 3 embodiment, a low-E or other coating 5 is provided betweensubstrate 1 and DLC coating 3 (i.e. the DLC coating of either the FIG. 1or FIG. 2 embodiment). However, DLC coating 3 is still on substrate 1 inthe FIG. 3 embodiment, along with a ta-C portion 7 of coating 3. Thus,the term “on” herein means that substrate 1 supports DLC coating 3 orany layer (e.g. 7, 8) thereof, regardless of whether or not otherlayer(s) 5 are provided therebetween. Thus, protective coating 3 may beprovided directly on substrate 1 as shown in FIGS. 1-2, or may beprovided on substrate 1 with a low-E or other coating(s) 5 therebetweenas shown in FIG. 3. Coating 5, instead of its illustrated position inFIG. 3, may also be provided on top of DLC coating 3 so that coating 3(of either the FIG. 1 or FIG. 2 embodiment) is located betweencoating(s) 5 and substrate 1. In still other embodiments, a DLC coating3 may be provided on both sides of a low-E coating 5.

Exemplar coatings (in full or any portion of these coatings) that may beused as low-E or other coating(s) 5, either on top of or below DLCcoating 3, are shown and/or described in any of U.S. Pat. Nos.5,837,108, 5,800,933, 5,770,321, 5,557,462, 5,514,476, 5,425,861,5,344,718, 5,376,455, 5,298,048, 5,242,560, 5,229,194, 5,188,887 and4,960,645, which are all hereby incorporated herein by reference. Simplesilicon oxide and/or silicon nitride coating(s) may also be used ascoating(s) 5.

As will be discussed in more detail below, highly tetrahedral amorphouscarbon (ta-C) layer(s) 7 is a special form of diamond-like carbon (DLC),and includes at least about 35% sp³ carbon-carbon bonds (i.e. it ishighly tetrahedral). In certain embodiments of this invention, ta-Clayer(s) 7 has at least about 35% sp³ carbon-carbon bonds of the totalsp bonds in the layer, more preferably at least about 70%, and mostpreferably at least about 80% sp³ carbon-carbon bonds so as to increasethe density of layer 7 and its bonding strength. The amounts of sp³bonds may be measured using Raman finger-printing and/or electron energyloss spectroscopy. The high amount of sp³ bonds increases the density oflayer thereby allowing it to prevent soda diffusion to the surface ofthe coated article.

Ta—C layer 7 forms the entirety of DLC coating 3 in the FIG. 2embodiment, and ta-C layer 7 forms only a portion of DLC coating 3 inthe FIG. 1 embodiment. This is because interfacial amorphous carbonlayer 8 in the FIG. 1 embodiment sometimes has a density less than about2.4 grams per cubic centimeter and/or less than about 35% sp³carbon-carbon bonds. However, it is noted that DLC coating 3 has aninterfacial layer immediately adjacent substrate 1 in each of the FIG. 1and FIG. 2 embodiments, with the difference being that the interfaciallayer in the FIG. 2 embodiment has a density of at least about 2.4 gramsper cubic centimeter and at least about 35% sp³ (more preferably atleast about 70%, and most preferably at least about 80%) carbon-carbonbonds. Thus, layer 7 herein refers to both layer 7 as illustrated in theFIG. 1 embodiment as well as DLC coating 3 in the FIG. 2 embodiment.

At least some carbon atoms of DLC coating 3, and/or some sp² and/or sp³carbon-carbon bonds, are provided in fissures or cracks in a surface(e.g. top surface) of the glass substrate, or may penetrate the glasssurface of substrate 1 itself or the surface of growing DLC, so as tostrongly bond coating 3 to substrate 1. Subimplantation of carbon atomsinto the surface of substrate 1 enables coating 3 to be strongly bondedto substrate 1.

For purposes of simplicity, FIG. 4 illustrates an exemplar sp³carbon-carbon or C—C bond (i.e. carbon to carbon diamond like bond) incoating 3, FIG. 4 an exemplar sp² C—C bond in coating 3, and FIG. 5 anexemplar sp.

The provision of dense (density of at least about 2.4 gm/cm³) ta-C layer7 on soda inclusive glass substrate 1 reduces the amount of soda whichcan exit the substrate or reach the surface of the substrate or coatedarticle (i.e. ta-C limits sodium diffusion from the substrate). Thus,less soda is allowed to react with water or other material(s) on thesurface of the article. The end result is that the provision of ta-Clayer 7 on the substrate reduces stains and/or corrosion on the glassarticle which can form over time. The large number of sp³ carbon-carbonbonds increases the density of layer 7 and allows the layer to repelwater and minimize soda diffusion from soda inclusive glass.

Coating(s) 3, and layer(s) 7, 8, also strengthen the glass article,reduce stress at the bonding surfaces between coating 3 and substrate 1,and provide a solid lubricant surface on the article when coating 3 islocated at a surface of the article. Coating(s) 3 and/or layer 7 mayincludes a top layer portion (e.g. the top 3 to 15 Å) that is less densethan central areas of coating 3, thereby providing a solid lubricant atthe top surface of coating 3 furthest from the substrate so that thearticle is resistant to scratching. Ta—C layer 7 also providesresistance to water/moisture entering or coming into substrate 1.Coating 3, and thus ta-C layer 7, are preferably formed/depositedcontinuously across glass substrate 1, absent any pinholes or apertures.

In certain embodiments, layer 7 and/or 8 adjacent the glass substrate isdeposited at an ion energy that allows significant numbers of carbonatoms to penetrate cracks in the glass surface as shown in FIG. 8. Thesmall size of carbon atoms and the ion energy utilized preventsubstantial water from reaching the tip of the crack(s). Thisstrengthens the glass in the long term by slowing down and/or stoppingthe rupture of silicon-oxygen bonds at crack tips caused by waterexposure.

Advantages associated with certain embodiments of this inventioninclude: (i) coated window articles that can shed water in differentenvironments (e.g. automotive windows such as backlites and windshields,or commercial and residential windows); (ii) anti-fog coated articlesthat are resistant to fogging up; (iii) strengthened coated windows;(iv) abrasion resistant coated windows; (v) coated articles that canrepel dirt; and (vi) coated glass articles less susceptible to visiblecorrosion on surfaces thereof. For example, in automotive windowembodiments, the outer surface of substrate 1 exposed to the environmentis coated with coating 3 in accordance with any of the FIG. 1-3embodiments. In anti-fog automotive embodiments, the inner surface ofautomotive window substrates 1 may be coated with coating 3 inaccordance with any of the FIG. 1-3 embodiments.

In certain embodiments, coating 3 is at least about 70% transparent toor transmissive of visible light rays, preferably at least about 80%,and most preferably at least about 90% transparent to visible lightrays.

In certain embodiments, DLC coating 3 (and thus layer 7 in the FIG. 2embodiment) may be from about 30 to 3,000 Å thick, most preferably fromabout 50 to 300 Å thick. As for glass substrate 1, it may be from about1.5 to 5.0 mm thick, preferably from about 2.3 to 4.8 mm thick, and mostpreferably from about 3.7 to 4.8 mm thick. Ta—C layer 7, in certainembodiments, has a density of at least about 2.4 grams per cubiccentimeter, more preferably from about 2.4 to 3.4 gm/cm³, and mostpreferably from about 2.7 to 3.0 gm/cm³.

Substrate 1 includes soda or Na₂O in certain embodiments of thisinvention. Thus, ta-C layer(s) 7 minimize the amount of soda that canreach the surface of the coated article and cause stains/corrosion. Incertain embodiments, substrate 1 includes, on a weight basis, from about60-80% SiO₂, from about 10-20% Na₂O, from about 0-16% CaO, from about0-10% K₂O, from about 0-10% MgO, and from about 0-5% Al₂O₃. In certainother embodiments, substrate 1 may be soda lime silica glass including,on a weight basis, from about 66-75% SiO₂, from about 10-20% Na₂O, fromabout 5-15% CaO, from about 0-5% MgO, from about 0-5% Al₂O₃, and fromabout 0-5% K₂O. Most preferably, substrate 1 is soda lime silica glassincluding, by weight, from about 70-74% SiO₂, from about 12-16% Na₂O,from about 7-12% CaO, from about 3.5 to 4.5% MgO, from about 0 to 2.0%Al₂O₃, from about 0-5% K₂O, and from about 0.08 to 0.15% iron oxide.Soda lime silica glass according to any of the above embodiments mayhave a density of from about 150 to 160 pounds per cubic foot(preferably about 156), an average short term bending strength of fromabout 6,500 to 7,500 psi (preferably about 7,000 psi), a specific heat(0-100 degrees C.) of about 0.20 Btu/lbF, a softening point of fromabout 1330 to 1345 degrees F. a thermal conductivity of from about 0.52to 0.57 Btu/hrftF, and a coefficient of linear expansion (roomtemperature to 350 degrees C.) of from about 4.7 to 5.0×10⁻⁶ degrees F.In certain embodiments, any glass disclosed in U.S. Pat. No. 5,214,008or U.S. Pat. No. 5,877,103, each incorporated herein by reference, maybe used as substrate 1. Also, soda lime silica float glass availablefrom Guardian Industries Corp., Auburn Hills, Mich., may be used assubstrate 1.

Any such aforesaid glass substrate 1 may be, for example, green, blue orgrey in color when appropriate colorant(s) are provided in the glass.

In certain other embodiments of this invention, substrate 1 may be ofborosilicate glass, or of substantially transparent plastic. In certainborosilicate embodiments, the substrate 1 may include from about 75-85%SiO₂, from about 0-5% Na₂O, from about 0 to 4% Al₂O₃, from about 0-5%K₂O, from about 8-15% B₂O₃, and from about 0-5% Li₂C.

In still further embodiments, an automotive window (e.g. windshield orside window) including any of the above glass substrates laminated to aplastic substrate may combine to make up substrate 1, with the coating 3of any of the FIGS. 1-3 embodiments provided on either or both sides ofsuch a window. Other embodiments would have substrate 1 made up of asheet of soda lime silica glass laminated to a plastic sheet forautomotive window purpose, with coating(s) 3 of any of the FIG. 1-3embodiments on the inner side of the substrate bonded to the plastic. Inother embodiments, substrate 1 may include first and second glass sheetsof any of the above mentioned glass materials laminated to one another,for use in window (e.g. automotive windshield, residential window,commercial window, automotive side window, automotive backlite or backwindow, etc.) and other similar environments.

In certain embodiments, coating 3 and/or ta-C layer 7 may have anaverage hardness of from about 30-80 GPa (most preferably from about40-75 GPa), and a bandgap of from about 1.8 to 2.2 eV. It is noted thatthe hardness and density of coating 3 and/or layers 7, 8 thereof may beadjusted by varying the ion energy of the depositing apparatus orprocess described below.

When substrate 1 of any of the aforesaid materials is coated with atleast DLC coating 3 according to any of the FIGS. 1-3 embodiments, theresulting coated article has the following characteristics in certainembodiments: visible transmittance (Ill. A) greater than about 60%(preferably greater than about 70%), UV (ultraviolet) transmittance lessthan about 38%, total solar transmittance less than about 45%, and IR(infrared) transmittance less than about 35% (preferably less than about25%, and most preferably less than about 21%). Visible, “total solar”,UV, and IR transmittance measuring techniques are set forth in U.S. Pat.No. 5,800,933, as well as the '008 patent, incorporated herein byreference.

Diamond-like carbon (DLC) and the special tetrahedral amorphous carbon(ta-C) form 7 of DLC utilized in certain embodiments herein will now bedescribed in detail. All DLC 3 shown in drawings herein is amorphous.Ta—C 7 is amorphous and yet has substantial C—C tetrahedral (sp³-type)bonding and hence is termed tetrahedral amorphous carbon (ta-C) [orhighly ta-C] as it has at least 35% sp³ C—C bonds, preferably at leastabout 70% and most preferably at least about 80% sp³ C—C bonds.Diamond-like bonding gives this ta-C material gross physical propertiesapproaching those of diamond such as high hardness, high density andchemical inertness. However, ta-C also includes sp² C—C trigonal bondingand its optical and electronic properties are largely determined by thisbonding component. The fraction of sp² bonding, and thus the density, ina ta-C layer depends for example on the carbon ion energy used duringdeposition of coating 3 and/or layers 7 and 8. Properties of a given DLCcoating are a function of the fraction of sp³ to sp² bonding throughoutthe coating and thus throughout layers 7 and 8.

It is noted that the sp³ bonds discussed herein are sp³ carbon-carbonbonds which result in a high density coating 3 and/or 7 and are not sp³carbon-hydrogen bonds which do not provide as high of density.

Depending on the technique of deposition, many ta-C layers 7 hereincontain amounts of H (up to about 4%) which either include the C atom totake either a tetrahedral configuration or an sp² planar configurationor to be sp-hybridised within a linear polymeric-like form. In otherwords C—C, C—H and H—H correlations all contribute to the averagestructure of layers 7 in some embodiments.

In the case of ta-C which is fully or at least about 90% hydrogen-free,C—C bonding describes the local structure. Ta—C films also have somefraction of sp² or graphic bonding. The spatial distribution of trigonal(sp²) and tetrahedral carbon atoms may determine the bonding strength oflayer(s) 3 to glass, as well as the layer's density, strength, stress,etc. Tetrahedral amorphous carbon (ta-C) and its hydrogenated formta-C:H (which contains no more than about 10 at % or so H) have thehighest percentage of carbon-carbon (C—C) sp³ bonding, and are used aslayer 7 in the FIG. 1 embodiment and coating 3 in the FIG. 2 embodiment,and either of these in the FIG. 3 embodiment. This diamond-like bondingconfers upon ta-C 7 properties which are unrivaled by other forms of socalled DLC which have lower densities and/or greater proportion ofgraphitic sp² and polymeric sp C—C and C—H bonding.

Ta—C 7 has high density (at least about 2.4 grams per cubic centimeter),hardness, Young's modulus (700-800), as well as a low coefficient offriction (see Table 1 below).

TABLE 1 ta-C:H Properties c-Diamond ta-C (10% at H) Bandgap (eV)  5.452.0 2.2-2.5 Breakdown voltage (V cm-1) 100    25-35 30   10{circumflexover ( )}5 Dielectric Constant 5.5 4.5 4.7 Resistivity (ohm-cm) 10¹⁸ 10¹¹  10¹²  Thermal Conductivity 20   0.1 0.1 (Wcm⁻¹K⁻¹) Young's modulusGpa 1000    700-800 500    Hardness (Gpa) 100    30-80  5-80 Refractiveindex 2.4 2.0 1.6-1.9 Structure crystalline amorphous amorphousDeposition high temp CVD 0.1 um/hr low temp low temp condition/rate <200C. 20 A/s wetability contact angle 5 to 50 Max thickness >1 um <200 nm<200 nm stress limited Coefficient of Friction <0.2 single crystal <0.1 <0.1 

Methods of depositing coating 3 on substrate 1 are described below forcertain embodiments of this invention.

Prior to coating 3 being formed on the glass substrate, the top surfaceof substrate 1 is preferably cleaned by way of an ion beam utilizingoxygen gas in each of the FIGS. 1 and 2 embodiments. Oxygen gasphysically cleans the surface due to its atomic weight of from about28-40 amu, most preferably about 32. Substrate 1 may also be cleaned by,for example, sputter cleaning the substrate prior to actual depositionof ta-C or other DLC material. This cleaning may utilize oxygen and/orcarbon atoms, and can be at an ion energy of from about 800 to 1200 eV,most preferably about 1,000 eV.

In plasma ion beam embodiments for depositing coatings 3, 7 and/or 8,carbon ions may be energized to form a stream from plasma towardsubstrate 1 so that carbon from the ions is deposited on substrate 1. Anion beam from gas phase produces a beam of C+, CH+, C₂H, and/or C₂H₂+ions (i.e. carbon or carbon based radicals). Preferably, acetylenefeedstock gas (C₂H₂) is used to prevent or minimize polymerization andto obtain an appropriate energy to allow the ions to penetrate thesubstrate 1 surface and subimplant therein, thereby causing coating 3atoms to intermix with the surface of substrate 1 a few atom layersthereinto. Impact energy of ions for the bulk of coating 3 (e.g. layer 7in the FIGS. 1 and 2 embodiments) may be from about 100 to 200 eV percarbon atom, preferably from about 100-150 eV, to cause dense sp³ C—Cbonds to form in the DLC layer. The ions impact the substrate with thisenergy which promotes formation of sp³ carbon-carbon bonds. The impactenergy of the energetic carbon ions may be within a range to promoteformation of the desired lattice structure, such bonds in an interfacingportion (e.g. layer 8 in the FIG. 1 embodiment) of coating 3 apparentlybeing formed at least in part by subimplantation into the substrate asshown in FIG. 7. The stream may be optionally composed of ions havingapproximately uniform weight, so that impact energy will beapproximately uniform. Effectively, the energetic ions impact on thegrowing film surface and/or substrate 1 and are driven into the growingfilm and/or substrate 1 to cause densification. Coating 3, andespecially layer 7, are preferably free of pinholes, to achievesatisfactory water repulsion and suppression of soda diffusion.

Thus, the C—C sp³ bonding is preferably formed by having a predeterminedrange of ion energy prior to reaching substrate 1, or prior to reachingta-C growing on the substrate. The optimal ion energy window for ta-Clayer 7 formation in the FIGS. 1 and 2 embodiments is from about 100-200eV (preferably from about 100-150 eV, and most preferably from about100-140 eV) per carbon ion. At these energies, films 7 (i.e. layer 3 inthe FIG. 2 embodiment) emulate diamond.

However, compressive stresses can develop in ta-C when being depositedat 100-150 eV. Such stress can reach as high as 10 Gpa and canpotentially cause delamination from many substrates. It has been foundthat these stresses can be controlled and decreased by increasing theion energy the deposition process to a range of from about 200-1,000 eV.The plasma ion beam source enables ion energy to be controlled withindifferent ranges in an industrial process for large area depositionutilized herein. The compressive stress in amorphous carbon is thusdecreased significantly at this higher ion energy range of 200-1,000 eV.

High stress is undesirable in the thin interfacing portion 8 of coating3 that directly contacts the surface of a glass substrate 1. Thus, forexample, the first 1-40% thickness (preferably the first 1-20% and mostpreferably the first 5-10% thickness) 8 of coating 3 is deposited onsubstrate 1 using high anti-stress energy levels of from about 200-1,000eV, preferably from about 400-500 eV. Then, after this initialinterfacing portion 8 of coating 3 has been grown, the ion energy in theion deposition process is decreased (either quickly or gradually whiledeposition continues) to about 100-200 eV, preferably from about 100-150eV, to grow the remainder ta-C layer 7 of coating 3.

For example, assume for exemplary purposes only with reference to FIG. 1that DLC coating 3 is 100 Å thick. The first 10 Å layer 8 of coating 3(i.e. interfacing portion 8) may be deposited using an ion energy offrom about 400 to 500 eV so that layer 8 of coating 3 that contacts thesurface of substrate 1 has reduced compressive stresses relative to theremainder 7 of coating 3. Interfacing portion 8 of coating 3 at leastpartially subimplants into the surface of substrate 1 to allowintermixing with the glass surface. In certain embodiments, only C ionsare used in the deposition of interfacing layer 8, with the gradedcomposition interface being mainly SiC. This interface 8 betweensubstrate 1 and coating 3 improves adhesion of coating 3 to substrate 1and the gradual composition change distributes strain in the interfacialregion instead of narrowly concentrating it. Layer 8 of DLC coating 3may or may not have a density of at least about 2.4 grams per cubiccentimeter in different embodiments, and may or may not have at leastabout 35%, 70%, or 80% sp³ carbon-carbon bonds in different embodiments.After the first 10 Å (i.e. layer 8) of coating 3 has been deposited,then the ion energy is gradually or quickly decreased to 100 to 150 eVfor the remainder [may be either ta-C or ta-C:H] 7 of coating 3 so thatlayer 7 has a higher density and a higher percentage of sp³ C—C bondsthan layer 8.

Thus, in certain embodiments, because of the adjustment in ion energyduring the deposition process, ta-C coating 3 in FIGS. 1-3 has differentdensities and different percentages of sp³ C—C bonds at different areastherein. However, at least a portion of coating 3 is a highlytetrahedral ta-C layer 7 having a density of at least about 2.4 gramsper cubic centimeter and at least about 35% sp³. The highly tetrahedralta-C portion is the portion furthest from substrate 1 in FIG. 1, but mayoptionally be at other areas of coating 3. In a similar manner, theportion of coating 3 having a lesser percentage of sp³ C—C bonds ispreferably the portion immediately adjacent substrate 1 (e.g.interfacing layer 8).

In certain embodiments, CH₄ may be used as a feedstock gas during thedeposition process instead of or in combination with the aforesaid C₂H₂gas.

Referring to FIG. 8, it is noted that the surface of a glass substratehas tiny cracks or microcracks defined therein. These cracks may weakenglass by orders of magnitude, especially when water seeps therein andruptures further bonds. Thus, another advantage of this invention isthat in certain embodiments amorphous carbon atoms and/or networks oflayer 7 or 8 fill in or collect in these small cracks because of thesmall size of carbon atoms (e.g. less than about 100 pm radius atomic,most preferably less than about 80 pm, and most preferably about 76.7pm) and because of the ion energy of 200 to 1,000 eV, preferably about400-500 eV, and momentum. This increases the mechanical strength of theglass. The nano cracks in the glass surface shown in FIG. 8 maysometimes be from about 0.4 nm to 1 nm in width. The inert nature andsize of the carbon atoms in these nonocracks will prevent water fromattacking bonds at the crack tip 14 and weakening the glass. The carbonatoms make their way to positions adjacent the tips 14 of these cracks,due to their size and energy. Tips 14 of these cracks are, typically,from about 0.5 to 50 nm below the glass substrate surface. The topsurface of layers 7 and/or 8 remains smooth and/or approximately flatwithin about less than 1.0 nm even above the cracks.

Carbon is now described generally, in many of its forms, to aid in theunderstanding of this invention.

Carbon has the ability to form structures based on directed covalentbonds in all three spatial dimensions. Two out of the six electrons of acarbon atom lie in the 1s core and hence do not participate in bonding,while the four remaining 2s and 2p electrons take part in chemicalbonding to neighboring atoms. The carbon atom's one 2s and three 2pelectron orbitals can hybridise in three different ways. This enablescarbon to exist as several allotropes. In nature, three allotropiccrystalline phase exists, namely diamond, graphite and the fullerenesand a plethora of non-crystalline forms.

For the diamond crystalline allotrope, in tetrahedral or sp³ bonding allthe four bonding electrons form σ bonds. The space lattice in diamond isshown in FIG. 4 where each carbon atom is tetrahedrally bonded to fourother carbon atoms by σ bonds of length 0.154 nm and bond angle of 109°53″. The strength of such a bond coupled with the fact that diamond is amacromolecule (with entirely covalent bonds) give diamond uniquephysical properties: high atomic density, transparency, extremehardness, exceptionally high thermal conductivity and extremely highelectrical resistivity (10¹⁶ Ω-cm)

The properties of graphite are governed by its trigonal bonding. Theouter 2s, 2p_(x) and 2p_(y) orbitals hybridise in a manner to give threeco-planar sp² orbitals which form a bonds and a p-type π orbital 2p_(z)perpendicular to the sp² orbital plane, as shown in FIG. 5. Graphiteconsists of hexagonal layers separated from each other by a distance of0.34 nm. Each carbon atom is bonded to three others by 0.142 nm long σbonds within an hexagonal plane. These planes are held together by weakvan der Waals bonding which explains why graphite is soft along the sp²plane.

As for fullerenes, it is known that C₆₀ and C₇₀ are the most accessiblemembers of the family of closed-cage molecules called fullerenes, formedentirely of carbon in the sp² hybridised state. Each fullerenes C_(n)consists of 12 pentagonal rings and m hexagonal rings such thatm=(n−20)/2 (satisfying Euler's Theorem). The σ bonds are wrapped suchthat the fullerene has a highly strained structure and the molecule isrigid.

As for amorphous carbon, there exists a class of carbon in themetastable state without any long range order. Material propertieschange when using different deposition techniques or even by varying thedeposition parameters within a single technique. In this category ofmaterials on one extreme we have ta-C (e.g. layer 7) which is the mostdiamond-like with up to 90% C—C sp³ bonding in certain preferredembodiments and on the other a-C (amorphous carbon), produced by thermalevaporation of carbon, in which more than 95% graphitic bonds areprevalent. In this respect, these two materials reflect the intrinsicdiversity of non-crystalline forms of carbon.

Amorphous materials, such as layer(s) 3, 7 and 8, are metastable solids.In an amorphous solid there exists a set of equilibrium positions aboutwhich atoms oscillate. The atoms in an amorphous material are oftenextended into a three dimensional network with the absence of orderbeyond the second nearest neighbor distance.

Referring again to ta-C layer 7, the sp³/sp² C—C bonded fraction orpercentage (%), e.g. in a vacuum arc deposition technique or techniquesused in the '477 patent or deposition techniques discussed above, can becontrolled by changing the energy of the incident C⁺ ions. The filmsdeposited being metastable in nature are under high compressive stress.The sp² hybridised carbon atoms are clustered and embedded within a sp³matrix. The extent of the latter bonding confers onto ta-C itsdiamond-like physical properties. The fraction of the sp² hybridisedatoms determines the extent of clustering. The degree of clustering,which is seen as a strain relief mechanism, implies that the π and π*states become delocalised to such an extent that they control theelectronic and optical properties of the films. At high density ofstates, the n bands merge with the σ states to form the conduction andvalence mobility band-edges. Their lower density tail states arelocalised giving a pseudo-gap. The term “tetrahedral amorphous carbon(ta-C)” is thus used to distinguish this highly tetrahedral materialfrom other “diamond-like carbon” which have C—C correlations mostly ofthe sp² type.

The sp³ bonding in coatings 3 is believed to arise from a densificationprocess under energetic ion bombardment conditions. Hybridisation of thecarbon atom is expected to adjust to the local density, becoming moresp³ if the density is high and more sp² if low. This can occur if anincident ion penetrates the first atomic layer and then enters aninterstitial subsurface position. The local bonding then reforms aroundthis atom and its neighbours to adopt the most appropriatehybridisation. High energy ions in principle can penetrate the surfacelayer of the substrate or growing DLC, increase the density of deeperlayers which then forces sp³ bonding. Ions of lower energy than thepenetration threshold only append to the surface forming sp² bonded a-C.

Coated articles according to any of the aforesaid embodiments may beused, for example, in the context of automotive windshields, automotiveback windows, automotive side windows, architectural glass, IG glassunits, residential or commercial windows, and the like.

In any of the aforesaid embodiments, a layer of non-porous tungstendisulfide (WS₂) 12 may be provided on top of layer 7 to prevent the DLCfrom burning off upon exposure to air if taken to high temperaturesafter the coating deposition. Layer 12 (e.g. see FIG. 8) may be appliedby plasma spraying to a thickness of from about 300 to 10,000 Å. WS₂layer 12 is removeable in certain embodiments. Other suitable materialsmay instead be used for layer 12.

Once given the above disclosure, many other features, modifications, andimprovements will become apparent to the skilled artisan. Such otherfeatures, modifications, and improvements are, therefore, considered tobe a part of this invention, the scope of which is to be determined bythe following claims.

1-27. (canceled)
 28. A method of making a coated article, the methodcomprising: forming a layer comprising carbon on a glass substrate; andforming a layer comprising tungsten disulfide on the glass substrateover the layer comprising carbon to prevent the layer comprising carbonfrom burning off upon exposure to air if taken to high temperatures. 29.The method of claim 28, wherein a low-E coating is provided between theglass substrate and the layer comprising carbon.
 30. The method of claim28, wherein the layer comprising carbon comprises DLC and has an averagedensity of at least 2.4 gm/cm3.
 31. The method of claim 28, wherein thelayer comprising carbon further includes hydrogen.